We report on CO 2 electroreduction activity and selectivity of a polycrystalline AgZn foil in aqueous bicarbonate electrolyte. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements show that the alloy foil was slightly enriched in zinc both at the surface and in the bulk, with a surface alloy composition of 61.3±5.4 at % zinc and with Ag 5Zn 8 as the most prominent bulk phase. AgZn is active for CO 2 reduction; CO is the main product, likely due to the weak CO binding energy of the surface, with methane and methanol emerging as minor products. Compared to pure silver and pure zinc foils, enhancements in activity and selectivity for methane and methanol are observed. A five-fold increase is observed in the combined partial current densities for methane and methanol at –1.43 V vs. the reversible hydrogen electrode (RHE), representing a four- to six-fold increase in faradaic efficiency. Here, such enhancements indicate the existence of a synergistic effect between silver and zinc at the surface of the alloy that contributes to the enhanced formation of further reduced products.

@article{osti_1369412,
title = {Carbon Dioxide Electroreduction using a Silver-Zinc Alloy [CO2 Electroreduction on a Ag-Zn Alloy]},
author = {Hatsukade, Toru and Kuhl, Kendra P. and Cave, Etosha R. and Abram, David N. and Feaster, Jeremy T. and Jongerius, Anna L. and Hahn, Christopher and Jaramillo, Thomas F.},
abstractNote = {We report on CO2 electroreduction activity and selectivity of a polycrystalline AgZn foil in aqueous bicarbonate electrolyte. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements show that the alloy foil was slightly enriched in zinc both at the surface and in the bulk, with a surface alloy composition of 61.3±5.4 at % zinc and with Ag5Zn8 as the most prominent bulk phase. AgZn is active for CO2 reduction; CO is the main product, likely due to the weak CO binding energy of the surface, with methane and methanol emerging as minor products. Compared to pure silver and pure zinc foils, enhancements in activity and selectivity for methane and methanol are observed. A five-fold increase is observed in the combined partial current densities for methane and methanol at –1.43 V vs. the reversible hydrogen electrode (RHE), representing a four- to six-fold increase in faradaic efficiency. Here, such enhancements indicate the existence of a synergistic effect between silver and zinc at the surface of the alloy that contributes to the enhanced formation of further reduced products.},
doi = {10.1002/ente.201700087},
journal = {Energy Technology},
number = 6,
volume = 5,
place = {United States},
year = {2017},
month = {2}
}

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO 2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO 2 reduction. Here in this paper, we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site –1 s –1 and a Faradaic efficiency as high as 95% for CO 2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in anmore » organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO 2. This represents the first example of a transition-metal complex for CO 2 electroreduction catalysis with its metal center being redox-innocent under working conditions.« less

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO 2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO 2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO 2 electroreduction to CO at -1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While themore » Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO 2. This represents the first example of a transition-metal complex for CO 2 electroreduction catalysis with its metal center being redox-innocent under working conditions.« less

Analysis of the CO 2 adsorption properties of a well-known series of metal–organic frameworks M 2(dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO 2 adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO 2 within many of these materials while systematically varying both the amount of CO 2 and the temperature. Unlike previous studies, wemore » show that CO 2 adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO 2 adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO 2. For the weaker CO 2 adsorbents, significant elongation of the metal–O(CO 2) distances are observed and diffraction experiments additionally reveal that secondary CO 2 adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contribute to adsorption behavior at ambient temperature. In conclusion, density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO 2 angles and trends in relative geometric properties and heats of adsorption in the M 2(dobdc)–CO 2 adducts.« less

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2H 4) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towardsmore » C 2H 4 generation vs CH 4, with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.« less

Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less